EP1334220A1 - Materiau pour substrats soumis a des contraintes thermiques - Google Patents

Materiau pour substrats soumis a des contraintes thermiques

Info

Publication number
EP1334220A1
EP1334220A1 EP01996641A EP01996641A EP1334220A1 EP 1334220 A1 EP1334220 A1 EP 1334220A1 EP 01996641 A EP01996641 A EP 01996641A EP 01996641 A EP01996641 A EP 01996641A EP 1334220 A1 EP1334220 A1 EP 1334220A1
Authority
EP
European Patent Office
Prior art keywords
layer
component
material according
group
thermal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP01996641A
Other languages
German (de)
English (en)
Other versions
EP1334220B1 (fr
Inventor
Markus Dietrich
Robert Vassen
Detlev STÖVER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Forschungszentrum Juelich GmbH
Original Assignee
Forschungszentrum Juelich GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Forschungszentrum Juelich GmbH filed Critical Forschungszentrum Juelich GmbH
Publication of EP1334220A1 publication Critical patent/EP1334220A1/fr
Application granted granted Critical
Publication of EP1334220B1 publication Critical patent/EP1334220B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64G—COSMONAUTICS; VEHICLES OR EQUIPMENT THEREFOR
    • B64G1/00—Cosmonautic vehicles
    • B64G1/22—Parts of, or equipment specially adapted for fitting in or to, cosmonautic vehicles
    • B64G1/52—Protection, safety or emergency devices; Survival aids
    • B64G1/58—Thermal protection, e.g. heat shields
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64G—COSMONAUTICS; VEHICLES OR EQUIPMENT THEREFOR
    • B64G1/00—Cosmonautic vehicles
    • B64G1/22—Parts of, or equipment specially adapted for fitting in or to, cosmonautic vehicles
    • B64G1/226—Special coatings for spacecraft
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • Y10T428/12618—Plural oxides

Definitions

  • the invention relates to a material based on perovskites for thermal insulation layers for the protection of temperature-stressed substrates, in particular for use in a gas turbine.
  • thermal insulation layers which usually consist of yttrium-stabilized zirconium oxide (YSZ).
  • a further increase to over 1300 ° C is aimed at, but cannot be achieved with the usual materials, in particular with YSZ.
  • the zirconium oxide deposited via plasma spraying or electron beam evaporation is subject to a phase change at temperatures above 1200 ° C, which increases within the operating time damage to the layer.
  • higher surface temperatures also lead to higher temperatures in the adhesion promoter layer and the substrate. These temperature increases also lead to accelerated damage to the composite material.
  • the object of the invention is to provide a material for a thermal barrier coating which fulfills the requirements of a low thermal conductivity, a high coefficient of thermal expansion and at the same time a phase stability up to temperatures above 1300 ° C. Furthermore, it is an object of the invention to create thermally stressed components with such a thermal barrier coating.
  • the oxides of the rare earth elements (Sc, Y), which are present in a perovskite structure, have particularly advantageous properties as a material for a thermal insulation layer.
  • the material according to the invention according to claim 1 is therefore characterized by a perovskite structure. This has the general formula AB0 3 .
  • the layer has at least one element from the group of lanthanides for the A or B position.
  • the group of lanthanides together with the elements scandium and yttrium is also called the group of rare earths (SE).
  • SE rare earths
  • the lanthanides include the elements with atomic numbers 57 to 71 in the periodic table of the elements.
  • a perovskite is therefore advantageously formed when the A position is occupied by the large cations of La, Ce or Nd in the material according to claim 2, and the B position z. B. is taken up by the cations of Yb, Lu, Er or Tm.
  • Another advantageous embodiment of the material provides a mixed perovskite in which the A and / or B positions are occupied by at least two different lanthanides.
  • the advantageous perovskite structure of the material according to the invention is characterized in particular by a high melting temperature.
  • the melting temperatures for the material, depending on the material are above 1800 ° C, in particular even above 2000 ° C. Up to the range in which the material reaches its melting temperature, such a material advantageously shows no phase change, and can therefore be used for corresponding purposes, in particular as a thermal barrier coating.
  • the material has a coefficient of thermal expansion of more than 8.5 * 10 "6 K " 1 .
  • a thermal conductivity of less than 2.2 W / mk is also advantageous.
  • a material with these properties is particularly suitable as a thermal barrier coating on a metallic substrate, since the adapted coefficient of thermal expansion reduces mechanical stresses between the two materials when the temperature rises, and the low thermal conductivity regularly prevents the substrate from overheating.
  • the component according to the invention has a layer on the surface made of a material according to one of claims 1 to 8.
  • Such a layer serves as a very effective thermal insulation layer for temperature-stressed components, which can withstand temperatures well above 1200 ° C without phase change. Due to the low thermal conductivity of this layer, high temperatures are regularly kept away from the component surface. This leads to a more efficient operation of the machines and / or to an extended service life of the component.
  • the material of the component and that of the layer advantageously have a similar coefficient of thermal expansion. This prevents thermally induced stresses from causing the layer to flake off the component surface.
  • At least one further layer is advantageously arranged between the layer according to the invention and the component, which, for example as an adhesion promoter layer, improves the adhesion between the individual layers and acts as oxidation protection for the substrate.
  • M means either nickel or cobalt
  • Cr is chrome
  • AI stands for aluminum
  • Y means yttrium.
  • An adhesion promoter layer made of this material is particularly temperature-resistant and advantageously adapted to the thermal expansion coefficients of the adjacent layers.
  • An intermediate layer made of an aluminide is also advantageous.
  • the material according to the invention can also advantageously be used as the top layer in a multi-layer system which is applied to a substrate.
  • This multi-layer system can consist of one HVS and at least two further layers exist. In the simplest case, this would be a two-layer system consisting of a first YSZ layer directly on the adhesion promoter layer and a further oxide layer, such as, for example, B. La 2 Zr 2 0 7 , as a second layer.
  • a suitable embodiment of the component according to claim 13 has a layer on the surface in which the concentration of lanthanides increases from the component / layer interface to the surface of the layer. This layer thus has a concentration gradient with respect to the lanthanides.
  • the thermal barrier coating is advantageously arranged on the surface of components of a gas turbine. This means that such gas turbines can also be operated at higher gas temperatures, especially above 1200 ° C. Higher gas temperatures advantageously mean an improvement in the efficiency of a gas turbine.
  • the materials of lanthanide perovskites according to the invention regularly have a high melting temperature> 2000 ° C. and show no phase change in the range from room temperature to the melting temperature. Their thermal conductivity is very low. With 1.45 W / mK is it z. B. with the LaYb0 3 clearly below that of the YSZ (2.1 W / mK) as today's standard WDS material.
  • the thermal expansion coefficient of LaYb0 3 was measured at 10 * 10 "6 K " 1 . It is therefore very large for a ceramic, so that the difference to the metallic substrate material (component) on which the layers are sprayed on can be kept small. This enables the thermally induced stresses in the thermal insulation layer to be reduced.
  • the peculiarity of the rare earth perovskites is the continuous interchangeability of the rare earth ions at the A position and those at the B position, since the SE ions are very similar in their external electronic structure. So z. B. La in LaYb0 3 can be continuously replaced by Nd or Yb by Lu.
  • the substituted perovskites are then described by the general formula A ' X A'' ⁇ _ x B' y B '' ⁇ - y 0 3 with 0 ⁇ x, y ⁇ 1. This variation enables a change in the thermophysical properties of the rare earth perovskites and thus their optimization.
  • Thermal insulation layers based on the lananide perovskites according to the invention can be produced in various ways:
  • the LaYb0 3 is represented by a solid-state reaction corresponding to La 2 0 3 + Yb 2 0 3 -> 2 LaYb0 3 .
  • the starting powders are ground in a ball mill under ethanol and then reaction-annealed at 1400 ° C. A flowable powder is then produced by spray drying.
  • the ceramic layer of lanthanide perovskite is then sprayed onto the bonding agent layer (HVS) in a thickness of approximately 0.3 mm by means of APS (atmospheric plasma spraying).
  • the LaLu0 3 powder is produced by spray drying an aqueous La (N0 3 ) 3 and Lu (N0 3 ) 3 solution with subsequent calcining at 1400 ° C. From this powder Ingots are manufactured for the EB-PVD (electron beam physical vapor deposition, electron beam PVD) process.
  • EB-PVD electron beam physical vapor deposition, electron beam PVD
  • the substrate provided with the adhesion promoter layer is coated with the LaLu0 3 ingot over EB-PVD.
  • a YSZ layer is then first applied to this adhesion promoter layer by means of APS and then a PrLu0 3 layer is applied using the same method. It is also possible to inject the two oxides in a continuous concentration gradient from YSZ to PrLu0 3 and thus to produce a graded WDS.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Ceramic Engineering (AREA)
  • Emergency Medicine (AREA)
  • Remote Sensing (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Critical Care (AREA)
  • Manufacturing & Machinery (AREA)
  • General Health & Medical Sciences (AREA)
  • Structural Engineering (AREA)
  • Aviation & Aerospace Engineering (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Laminated Bodies (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Organic Insulating Materials (AREA)
EP01996641A 2000-11-15 2001-11-08 Materiau pour substrats soumis a des contraintes thermiques Expired - Lifetime EP1334220B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10056617A DE10056617C2 (de) 2000-11-15 2000-11-15 Werkstoff für temperaturbelastete Substrate
DE10056617 2000-11-15
PCT/DE2001/004228 WO2002040745A1 (fr) 2000-11-15 2001-11-08 Materiau pour substrats soumis a des contraintes thermiques

Publications (2)

Publication Number Publication Date
EP1334220A1 true EP1334220A1 (fr) 2003-08-13
EP1334220B1 EP1334220B1 (fr) 2004-09-08

Family

ID=7663402

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01996641A Expired - Lifetime EP1334220B1 (fr) 2000-11-15 2001-11-08 Materiau pour substrats soumis a des contraintes thermiques

Country Status (6)

Country Link
US (1) US6821656B2 (fr)
EP (1) EP1334220B1 (fr)
JP (1) JP4133324B2 (fr)
AT (1) ATE275647T1 (fr)
DE (2) DE10056617C2 (fr)
WO (1) WO2002040745A1 (fr)

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EA029490B1 (ru) 2011-11-29 2018-04-30 Силурия Текнолоджиз, Инк. Катализаторы из нанопроволоки и способы их применения и получения
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Also Published As

Publication number Publication date
DE10056617C2 (de) 2002-12-12
JP4133324B2 (ja) 2008-08-13
US6821656B2 (en) 2004-11-23
DE10056617A1 (de) 2002-05-29
ATE275647T1 (de) 2004-09-15
JP2004514064A (ja) 2004-05-13
DE50103564D1 (de) 2004-10-14
US20040043261A1 (en) 2004-03-04
WO2002040745A1 (fr) 2002-05-23
EP1334220B1 (fr) 2004-09-08

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